Relay orbital hybridization on MnMoO4 catalysts for durable lithium–oxygen batteries

MnMoO 4 holds great promise as a cathode material for lithium–oxygen batteries (LOBs), but its poor conductivity and weak interaction with oxygenated intermediates substantially impede its electrocatalytic properties. Herein, electron-deficient P atoms were incorporated with MnMoO 4 hollow nanospheres (P-doped MnMoO 4 ) to realize internal orbital interactions between Mo 4d and P 3p, activating external orbital hybridization between catalysts and LiO 2 during cycling. This relay orbital hybridization not only promoted charge transfer but also optimized the adsorption and desorption abilities of catalysts toward LiO 2 , thereby reducing the reaction energy barriers. Consequently, LOBs with P-doped MnMoO 4 cathode catalysts sustained steady operation for 380 cycles under 1000 mA g –1 , which is even better than some of their noble metal counterparts and points to their commercial promise for use in future large-scale applications. This work provides general guidance for constructing relay orbital hybridization through P doping on catalysts for LOBs and other electrocatalytic systems. • Introducing phosphorus heteroatoms into MnMoO 4 lattices induces a relay catalytic effect from inside to outside, leading to intramolecular d–p orbital hybridization and intermolecular orbital hybridization. • The effects of relay orbital hybridization from Mo and P for P-doped MnMoO 4 and LiO 2 in cathode reactions are intensively investigated using density functional theory calculations. • Lithium–oxygen batteries with P-doped MnMoO 4 hollow nanospheres exhibit lower overpotentials and a long cycling lifespan, outperforming some of their benchmark noble metal counterparts.